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| United States Patent |
5,068,274
|
|
Efner
|
November 26, 1991
|
Secondary amides in polyethylene terephthalate molding compositions
Abstract
Reinforced polyethylene terephthalate molding resin compositions with
glossy surface are provided which crystallize rapidly after being
injection molded and which have engineering resin performance
characteristics. In addition to polyethylene terephthalate and glass
fibers, the compositions contain an aliphatic polyester, an ionic
hydrocarbon polymer, an antioxidant, and a secondary amide. Optionally,
the compositions may contain a portion of glass flakes, mica or other
filler. The compounds can be flame retarded with a brominated polystyrene
and an antimonate without substantial change in properties.
| Inventors:
|
Efner; Howard F. (Bartlesville, OK)
|
| Assignee:
|
Phillips Petroleum Company (Bartlesville, OK)
|
| Appl. No.:
|
544498 |
| Filed:
|
July 19, 1990 |
| Current U.S. Class: |
524/230; 524/605; 525/444 |
| Intern'l Class: |
C08K 005/20 |
| Field of Search: |
524/230,210,605
525/444,170
|
References Cited
U.S. Patent Documents
| Re32334 | Jan., 1987 | Deyrup | 524/292.
|
| 3565852 | Feb., 1971 | Conix | 525/444.
|
| 4129715 | Dec., 1978 | Chen et al. | 528/67.
|
| 4223113 | Sep., 1980 | Bier et al. | 525/444.
|
| 4338243 | Jul., 1982 | Hecht et al. | 524/210.
|
| 4447572 | May., 1984 | Scharf et al. | 524/371.
|
| 4528346 | Jul., 1985 | Sugie et al. | 525/523.
|
| 4547547 | Oct., 1985 | Chen et al. | 524/538.
|
| 4769403 | Sep., 1988 | Luise | 524/410.
|
Primary Examiner: Hoke; Veronica P.
Attorney, Agent or Firm: Bennett; Morrison
Claims
That which is claimed is:
1. A composition comprising:
(a) about 30 to about 90 weight percent, based on the total weight of the
composition polyethylene terephthalate;
(b) about 5 to about 65 weight percent based on the total weight of the
composition filler;
(c) about 0.5 to 15 parts per hundred parts of (a) a normally liquid
aliphatic polyester having a number average molecular weight in the range
from about 7,500 to about 20,000 and which is a condensation product of an
alkanedioic acid containing from 8 to about 12 carbon atoms per molecule
and an alkanediol containing from 2 to about 5 carbon atoms per molecule;
(d) about 0.1 to about 3 parts per hundred parts of (a) a metal salt of an
ionic hydrocarbon copolymer of an alpha-olefin containing from 2 to about
5 carbon atoms per molecule and an alpha,beta-ethylenically unsaturated
carboxylic acid containing from 3 to about 5 carbon atoms per molecule in
which copolymer the neutralized anionic carboxyl groups are associated
with cations of said metal, said copolymer having a number average
molecular weight in excess of about 3,000 prior to neutralization, said
metal being selected from the group consisting of sodium and potassium;
(e) about 0.01 to 2 parts per hundred parts of (a) an antioxidant;
(f) about 0.1 to about 5 parts per hundred parts of (a) a secondary amide
described by the formula:
##STR4##
wherein R.sub.1 and R.sub.2 may be the same or different and represent
alkyl groups or unsaturated aliphatic groups containing from 8 to 36
carbon atoms, and wherein each said unsaturated group can have up to three
double bonds.
2. A composition according to claim 1 wherein:
said polyethylene terephthalate is present in an amount within the range of
about 35 to about 65 weight percent, based on total weight of the
composition;
said filler includes glass fibers, said glass fibers being present in an
amount within the range of about 0 to about 60 weight percent, based on
total weight of the composition;
said aliphatic polyester is present in an amount within the range of about
2.5 to about 10 pph resin;
said metal salt is present in an amount within the range of about 0.2 to
about 1.2 pph resin;
said antioxidant is present in an amount within the range of about 0.2 to
about 1.0 pph resin; and
said secondary amide is present in an amount of about 0.5 to about 3 pph
resin.
3. A composition as recited in claim 2 which additionally contains from
greater than 0 to about 50 pph resin of a flame retardant.
4. A composition as recited in claim 3 wherein said flame retardant
consists essentially of:
(i) brominated polystyrene having a molecular weight ranging from about
10,000 to about 400,000 and having a bromine content in the range of from
about 55 to about 75 weight percent based on the total weight of said
brominated polystyrene; and
(ii) an antimonate of at least one metal selected from Groups I, II or VII
of the Periodic Table, the weight ratio of said brominated polystyrene to
said antimonate being in the range from about 2:1 to 12:1.
5. A composition as recited in claim 4 wherein said antimonate is selected
from the group consisting of sodium antimonate, zinc antimonate, and
nickel antimonate.
6. A composition as recited in claim 5 wherein said antimonate comprises
sodium antimonate.
7. A composition as recited in claim 2 which additionally contains from
greater than 0 to about 10 weight percent based on total weight of the
composition of a colorant.
8. A composition as recited in claim 2 wherein said aliphatic polyester has
a molecular weight in the range from about 8,000 to about 10,000 and
comprises a condensation product of sebacic acid and 1,2-propanediol.
9. A composition as recited in claim 2 wherein said ionic hydrocarbon
copolymer is a copolymer of ethylene and an alpha,beta-ethylenically
unsaturated carboxylic acid selected from the group consisting of acrylic
acid, methacrylic acid, and mixtures thereof.
10. A composition as recited in claim 2 wherein said antioxidant is a
hindered phenol.
11. A composition as recited in claim 7 wherein said colorant is carbon
black.
12. A composition as recited in claim 3 wherein said aliphatic polyester
has a molecular weight in the range from about 8,000 to about 10,000 and
comprises a condensation product of sebacic acid and 1,2-propanediol.
13. A composition as recited in claim 3 wherein said ionic hydrocarbon
copolymer is a copolymer of ethylene and an alpha,beta-ethylenically
unsaturated carboxylic acid selected from the group consisting of acrylic
acid, methacrylic acid, and mixtures thereof.
14. A composition as recited in claim 3 wherein said antioxidant is a
hindered phenol.
15. A composition as recited in claim 3 which additionally contains from
greater than 0 to about 10 weight percent based on total weight of the
composition of a colorant.
16. A composition as recited in claim 15 wherein said colorant is carbon
black.
17. A composition according to claim 1 wherein said filler comprises a
mixture of mica and fiber glass.
18. A composition according to claim 1 wherein:
said polyethylene terephthalate is present in an amount within the range of
about 30 to about 90 weight percent based on total weight of the
composition;
said filler is present in an amount within the range of about 5 to about 65
weight percent, based on total weight of the composition, said filler
comprising a mixture of mica and fiber glass having a ratio of said mica
to said fiber glass from about 10:1 to about 1:10;
said aliphatic polyester is present in an amount within the range of about
0.5 to about 15 pph resin;
said metal salt is present in an amount within the range of about 0.1 to
about 3 pph resin;
said antioxidant is present in an amount within the range of about 0.01 to
about 2 pph resin; and
said secondary amide is present in an amount within the range of about 0.1
to about 5 pph resin.
19. A composition as recited in claim 18 which additionally contains from
greater than 0 to about 50 pph resin of a flame retardant.
20. A composition as recited in claim 19 wherein said flame retardant
consists essentially of:
(i) brominated polystyrene having a molecular weight ranging from about
10,000 to about 400,000 and having a bromine content in the range of from
about 55 to about 75 weight percent based on the total weight of said
brominated polystyrene; and
(ii) an antimonate of at least one metal selected from Groups I, II or VII
of the Periodic Table, the weight ratio of said brominated polystyrene to
said antimonate being in the range from about 1:1 to 20:1.
21. A composition as recited in claim 18 wherein said aliphatic polyester
has a molecular weight in the range from about 8,000 to about 10,000 and
comprises a condensation product of sebacic acid and 1,2-propanediol.
22. A composition as recited in claim 18 wherein said ionic hydrocarbon
copolymer is a copolymer of ethylene and an alpha,beta-ethylenically
unsaturated carboxylic acid selected from the group consisting of acrylic
acid, methacrylic acid, and mixtures thereof.
23. A composition as recited in claim 18 wherein said antioxidant is a
hindered phenol.
24. A composition as recited in claim 19 wherein said aliphatic polyester
has a molecular weight in the range from about 8,000 to about 10,000 and
comprises a condensation product of sebacic acid and 1,2-propanediol.
25. A composition as recited in claim 19 wherein said ionic hydrocarbon
copolymer is a copolymer of ethylene and an alpha,beta-ethylenically
unsaturated carboxylic acid selected from the group consisting of acrylic
acid, methacrylic acid, and mixtures thereof.
26. A composition as recited in claim 19 wherein said antioxidant is a
hindered phenol.
27. A composition as recited in claim 18 which additionally contains from
greater than 0 to about 10 weight percent based on total weight of the
composition of a colorant.
28. A composition as recited in claim 19 which additionally contains from
greater than 0 to about 10 weight percent based on total weight of the
composition of a colorant.
29. A composition as recited in claim 27 wherein said colorant is carbon
black.
30. A composition as recited in claim 28 wherein said colorant is carbon
black.
31. A process for preparing a composition comprising:
(a) about 30 to about 90 weight percent, based on the total weight of the
composition polyethylene terephthalate;
(b) about 5 to about 65 weight percent based on the total weight of the
composition filler;
(c) about 0.5 to 15 parts per hundred parts of (a) a normally liquid
aliphatic polyester having a number average molecular weight in the range
from about 7,500 to about 20,000 and which is a condensation product of an
alkanedioic acid containing from 8 to about 12 carbon atoms per molecule
and an alkanediol containing from 2 to about 5 carbon atoms per molecule;
(d) about 0.1 to about 3 parts per hundred parts of (a) a metal salt of an
ionic hydrocarbon copolymer of an alpha-olefin containing from 2 to about
5 carbon atoms per molecule and an alpha,beta-ethylenically unsaturated
carboxylic acid containing from 3 to about 5 carbon atoms per molecule in
which copolymer the carboxyl groups are associated with cations of said
metal, said copolymer having a number average molecular weight in excess
of about 3,000 prior to neutralization, said metal being selected from the
group consisting of sodium and potassium;
(e) about 0.01 to 2 parts per hundred parts of (a) an antioxidant;
(f) about 0.1 to about 5 parts per hundred parts of (a) a secondary amide
described by the formula:
##STR5##
wherein R.sub.1 and R.sub.2 may be the same or different and represent
alkyl groups or unsaturated aliphatic groups containing from 8 to 36
carbon atoms, and wherein each said unsaturated group can have up to three
double bonds;
said process comprising mixing components (a) through (f) and melt
extruding the mixture.
32. A process in accordance with claim 31 wherein:
said polyethylene terephthalate is present in an amount within the range of
about 35 to about 65 weight percent based on total weight of the
composition;
said filler comprises glass fibers, said glass fibers being present in an
amount within the range of about 0 to about 60 weight percent, based on
total weight of the composition;
said aliphatic polyester is present in an amount within the range of about
2.5 to about 10 pph resin;
said metal salt is present in an amount within the range of about 0.2 to
about 1.2 pph resin;
said antioxidant is present in an amount within the range of about 0.2 to
about 1.0 pph resin; and
said secondary amide is present in an amount within the range of about 0.5
to about 3 pph resin.
33. A process as recited in claim 32 wherein said polyethylene
terephthalate is premixed with said glass fibers before the resulting
mixture is admixed with the remaining components.
34. A process in accordance with claim 31 wherein said composition further
comprises:
(g) a flame retardant.
35. A process according to claim 31 wherein:
said polyethylene terephthalate is present in an amount within the range of
about 30 to about 90 weight percent based on total weight of the
composition;
said filler comprises glass fibers, said glass fibers being present in an
amount within the range of about 5 to about 65 weight percent based on
total weight of the composition;
said aliphatic polyester is present in an amount within the range of about
0.5 to about 15 pph resin;
said metal salt is present in an amount within the range of about 0.1 to
about 3 pph resin;
said antioxidant is present in an amount within the range of about 0.01 to
about 2 pph resin;
said secondary amide is present in an amount within the range of about 0.1
to about 5 pph resin; and
wherein said composition comprises in addition:
(g) from greater than 0 to about 50 pph resin of a flame retardant.
36. A process as recited in claim 35 wherein said polyethylene
terephthalate is premixed with said glass fibers before the resulting
mixture is admixed with the remaining components.
37. A process according to claim 31 wherein said composition comprises in
addition:
(g) a flame retardant; and
(h) a colorant.
38. A process according to claim 31 wherein:
said polyethylene terephthalate is present in an amount within the range of
about 30 to about 90 weight percent based on total weight of the
composition;
said filler comprises glass fibers, said glass fibers being present in an
amount within the range of about 5 to about 65 weight percent, based on
total weight of the composition;
said aliphatic polyester is present in an amount within the range of about
0.5 to about 15 pph resin;
said metal salt is present in an amount within the range of about 0.1 to
about 3 pph resin;
said antioxidant is present in an amount within the range of about 0.01 to
about 2 pph resin;
said secondary amide is present in an amount within the range of about 0.1
to about 5 pph resin; and
wherein said composition comprises in addition:
(g) from greater than 0 to about 50 pph resin of a flame retardant; and
(h) from greater than 0 to about 10 weight percent, based on total weight
of the composition, of a colorant.
39. A process according to claim 31 wherein said filler comprises a mixture
of mica and fiber glass.
40. A process in accordance to claim 31 wherein:
said polyethylene terephthalate is present in an amount within the range of
about 30 to about 90 weight percent, based on total weight of the
composition;
said filler is present in an amount within the range of about 5 to about 65
weight percent, based on total weight of the composition, said filler
comprises a mixture of mica and fiber glass having a ratio of said mica to
said fiber glass from about 10:1 to about 1:10;
said aliphatic polyester is present in an amount within the range of about
0.5 to about 15 pph resin;
said metal salt is present in an amount within the range of about 0.1 to
about 3 pph resin;
said antioxidant is present in an amount within the range of about 0.01 to
about 2 pph resin; and
said secondary amide is present in an amount within the range of about 0.1
to about 5 pph resin.
41. A process according to claim 31 wherein:
said filler comprises a mixture of mica and fiber glass; and
wherein said composition comprises in addition:
(g) a flame retardant.
42. A process in accordance with claim 31 wherein:
said polyethylene terephthalate is present in an amount within the range of
about 30 to about 90 weight percent, based on total weight of the
composition;
said filler is present in an amount within the range of about 5 to about 65
weight percent, based on total weight of the composition, said filler
comprising a mixture of mica and fiber glass having a ratio of said mica
to said fiber glass from about 10:1 to about 1:10;
said aliphatic polyester is present in an amount within the range of about
0.5 to about 15 pph resin;
said metal salt is present in an amount within the range of about 0.1 to
about 3 pph resin;
said antioxidant is present in an amount within the range of about 0.01 to
about 2 pph resin;
said secondary amide is present in an amount within the range of about 0.1
to about 5 pph resin; and
wherein said composition further comprises:
(g) from greater than 0 to about 50 pph resin of a flame retardant.
43. A process according to claim 31 wherein said composition further
comprises:
(g) a colorant.
44. A process according to claim 31 wherein:
said polyethylene terephthalate is present in an amount within the range of
about 30 to about 90 weight percent, based on total composition;
said filler is present in an amount within the range of about 5 to about 65
weight percent, based on total weight of the composition, said filler
comprising a mixture of mica and fiber glass having a ratio of said mica
to said fiber glass from about 10:1 to about 1:10;
said aliphatic polyester is present in an amount within the range of about
0.5 to about 15 pph resin;
said metal salt is present in an amount within the range of about 0.1 to
about 3 pph resin;
said antioxidant is present in an amount within the range of about 0.01 to
about 2 pph resin;
said secondary amide is present in an amount within the range of about 0.1
to about 5 pph resin; and
wherein said composition comprises in addition:
(g) from greater than 0 to about 10 weight percent, based on total weight
of the composition, of a colorant.
45. A process according to claim 31 wherein:
said filler comprises a mixture of mica and fiber glass; and
wherein said composition comprises in addition:
(g) a flame retardant; and
(h) a colorant.
46. A process according to claim 31 wherein:
said polyethylene terephthalate is present in an amount within the range of
about 30 to about 90 weight percent, based on total weight of the
composition;
said filler is present in an amount within the range of about 5 to about 65
weight percent, based on total weight of the composition, said filler
comprising a mixture of mica and fiber glass having a ratio of said mica
to said fiber glass from about 10:1 to about 1:10;
said aliphatic polyester is present in an amount within the range of about
0.5 to about 15 pph resin;
said metal salt is present in an amount within the range of about 0.1 to
about 3 pph resin;
said antioxidant is present in an amount within the range of about 0.01 to
about 2 pph resin;
said secondary amide is present in an amount within the range of about 0.1
to about 5 pph resin;
said composition comprising in addition:
(g) from greater than 0 to about 50 pph resin of a flame retardant; and
(h) from greater than 0 to about 10 weight percent, based on total weight
of the composition, of a colorant.
47. A process for making a molded article which comprises injecting into a
mold a composition comprising:
(a) about 30 to about 90 weight percent, based on the total weight of the
composition polyethylene terephthalate;
(b) about 5 to about 65 weight percent based on the total weight of the
composition filler;
(c) about 0.5 to 15 parts per hundred parts of (a) a normally liquid
aliphatic polyester having a number average molecular weight in the range
from about 7,500 to about 20,000 and which is a condensation product of an
alkanedioic acid containing from 8 to about 12 carbon atoms per molecule
and an alkanediol containing from 2 to about 5 carbon atoms per molecule;
(d) about 0.1 to about 3 parts per hundred parts of (a) a metal salt of an
ionic hydrocarbon copolymer of an alpha-olefin containing from 2 to about
5 carbon atoms per molecule and an alpha,beta-ethylenically unsaturated
carboxylic acid containing from 3 to about 5 carbon atoms per molecule in
which copolymer the neutralized anionic carboxyl groups are associated
with cations of said metal, said copolymer having a number average
molecular weight in excess of about 3,000 prior to neutralization, said
metal being selected from the group consisting of sodium and potassium;
(e) about 0.01 to 2 parts per hundred parts of (a) an antioxidant;
(f) about 0.1 to about 5 parts per hundred parts of (a) a secondary amide
described by the formula:
##STR6##
wherein R.sub.1 and R.sub.2 may be the same or different and represent
alkyl groups or unsaturated aliphatic groups containing from 8 to 36
carbon atoms, and wherein each said unsaturated group can have up to three
double bonds.
48. A process according to claim 47 wherein:
said polyethylene terephthalate is present in an amount within the range of
about 35 to about 65 weight percent based on total weight of the
composition;
said filler comprises glass fibers, said glass fibers being present in an
amount within the range of about 0 to about 60 weight percent, based on
total weight of the composition;
said aliphatic polyester is present in an amount within the range of about
2.5 to about 10 pph resin;
said metal salt is present in an amount within the range of about 0.2 to
about 1.2 pph resin;
said antioxidant is present in an amount within the range of about 0.2 to
about 1.0 pph resin; and
said secondary amide is present in an amount within the range of about 0.5
to about 3 pph resin.
49. A process in accordance with claim 47 wherein said composition further
comprises:
(g) a flame retardant.
50. A process according to claim 47 wherein:
said polyethylene terephthalate is present in an amount within the range of
about 30 to about 90 weight percent based on total weight of the
composition;
said filler comprises glass fibers, said glass fibers being present in an
amount within the range of about 5 to about 65 weight percent based on
total weight of the composition;
said aliphatic polyester is present in an amount within the range of about
0.5 to about 15 pph resin;
said metal salt is present in an amount within the range of about 0.1 to
about 3 pph resin;
said antioxidant is present in an amount within the range of about 0.01 to
about 2 pph resin;
said secondary amide is present in an amount within the range of about 0.1
to about 5 pph resin; and
wherein said composition comprises in addition:
(g) from greater than 0 to about 50 pph resin of a flame retardant.
51. A process according to claim 47 wherein said composition comprises in
addition:
(g) a colorant.
52. A process in accordance with claim 47 wherein:
said polyethylene terephthalate is present in an amount within the range of
about 30 to about 90 weight percent, based on total weight of the
composition;
said filler comprises glass fibers, said glass fibers being present in an
amount within the range of about 5 to about 65 weight percent, based on
total weight of the composition;
said aliphatic polyester is present in an amount within the range of about
0.5 to about 15 pph resin;
said metal salt is present in an amount within the range of about 0.1 to
about 3 pph resin;
said antioxidant is present in an amount within the range of about 0.01 to
about 2 pph resin;
said secondary amide is present in an amount within the range of about 0.1
to about 5 pph resin; and
wherein said composition comprises in addition:
(g) from greater than 0 to about 10 weight percent, based on total weight
of the composition, of a colorant.
53. A process according to claim 47 wherein said composition comprises in
addition:
(g) a flame retardant; and
(h) a colorant.
54. A process according to claim 47 wherein:
said polyethylene terephthalate is present in an amount within the range of
about 30 to about 90 weight percent based on total weight of the
composition;
said filler comprises glass fibers, said glass fibers being present in an
amount within the range of about 5 to about 65 weight percent based on
total weight of the composition;
said aliphatic polyester is present in an amount within the range of about
0.5 to about 15 pph resin;
said metal salt is present in an amount within the range of about 0.1 to
about 3 pph resin;
said antioxidant is present in an amount within the range of about 0.01 to
about 2 pph resin;
said secondary amide is present in an amount within the range of about 0.1
to about 5 pph resin; and
wherein said composition comprises in addition:
(g) from greater than 0 to about 50 pph resin of a flame retardant; and
(h) from greater than 0 to about 10 weight percent, based on total weight
of the composition, of a colorant.
55. A process according to claim 47 wherein:
said polyethylene terephthalate is present in an amount within the range of
about 30 to about 90 weight percent, based on total weight of the
composition; and
said filler comprises a mixture of mica and fiber glass.
56. A process according to claim 47 wherein:
said polyethylene terephthalate is present in an amount within the range of
about 30 to about 90 weight percent, based on total weight of the
composition;
said filler is present in an amount within the range of about 5 to about 65
weight percent, based on total weight of the composition, said filler
comprising a mixture of mica and fiber glass having a ratio of said mica
to said fiber glass from about 10:1 to about 1:10;
said aliphatic polyester is present in an amount within the range of about
0.5 to about 15 pph resin;
said metal salt is present in an amount within the range of about 0.1 to
about 3 pph resin;
said antioxidant is present in an amount within the range of about 0.01 to
about 2 pph resin; and
said secondary amide is present in an amount within the range of about 0.1
to about 5 pph resin.
57. A process according to claim 47 wherein said composition comprises in
addition:
(g) a flame retardant.
58. A process according to claim 47 wherein:
said polyethylene terephthalate is present in an amount within the range of
about 30 to about 90 weight percent, based on total weight of the
composition;
said filler is present in an amount within the range of about 5 to about 65
weight percent, based on total weight of the composition; said filler
comprises a mixture of mica and fiber glass having a ratio of said mica to
said fiber glass from about 10:1 to about 1:10;
said aliphatic polyester is present in an amount within the range of about
0.5 to about 15 pph resin;
said metal salt is present in an amount within the range of about 0.1 to
about 3 pph resin;
said antioxidant is present in an amount within the range of about 0.01 to
about 2 pph resin;
said secondary amide is present in an amount within the range of about 0.1
to about 5 pph resin; and
wherein said composition further comprises:
(g) from greater than 0 to about 50 pph resin of a flame retardant.
59. A process according to claim 47 wherein:
said polyethylene terephthalate is present in an amount within the range of
about 30 to about 90 weight percent, based on total weight of the
composition;
said filler comprises a mixture of mica and fiber glass; and
wherein said composition comprises in addition:
(g) a colorant.
60. A process according to claim 47 wherein:
said polyethylene terephthalate is present in an amount within the range of
about 30 to about 90 weight percent, based on total weight of the
composition;
said filler is present in an amount within the range of about 5 to about 65
weight percent, based on total weight of the composition, said filler
comprising a mixture of mica and fiber glass having a ratio of said mica
to said fiber glass from about 10:1 to about 1:10;
said aliphatic polyester is present in an amount within the range of about
0.5 to about 15 pph resin;
said metal salt is present in an amount within the range of about 0.1 to
about 3 pph resin;
said antioxidant is present in an amount within the range of about 0.01 to
about 2 pph resin;
said secondary amide is present in an amount within the range of about 0.1
to about 5 pph resin; and
wherein said composition comprises in addition:
(g) from greater than 0 to about 10 weight percent, based on total weight
of the composition, of a colorant.
61. A process according to claim 47 wherein:
said filler comprises a mixture of mica and fiber glass; and
wherein said composition comprises in addition:
(g) a flame retardant; and
(h) a colorant.
62. A process according to claim 47 wherein:
said polyethylene terephthalate is present in an amount within the range of
about 30 to about 90 weight percent, based on total weight of the
composition;
said filler is present in an amount within the range of about 5 to about 65
weight percent, based on total weight of the composition, said filler
comprising a mixture of mica and fiber glass having a ratio of said mica
to said fiber glass from about 10:1 to about 1:10;
said aliphatic polyester is present in an amount within the range of about
0.5 to about 15 pph resin;
said metal salt is present in an amount within the range of about 0.1 to
about 3 pph resin;
said antioxidant is present in an amount within the range of about 0.01 to
about 2 pph resin;
said secondary amide is present in an amount within the range of about 0.1
to about 5 pph resin; and
wherein said composition comprises in addition:
(g) from greater than 0 to about 50 pph resin of a flame retardant; and
(h) from greater than 0 to about 10 weight percent, based on total weight
of the composition, of a colorant.
63. A molded article produced by the process of claim 47.
64. A molded article produced by the process of claim 49.
65. A molded article produced by the process of claim 51.
66. A molded article produced by the process of claim 53.
67. A molded article produced by the process of claim 55.
68. A molded article produced by the process of claim 57.
69. A molded article produced by the process of claim 59.
70. A molded article produced by the process of claim 61.
Description
BACKGROUND OF THE INVENTION
This invention relates to reinforced polyethylene terephthalate molding
compositions.
Polyethylene terephthalate molding compositions which are reinforced with
glass fibers, asbestos fibers, or other fibrous mineral material are known
to either crystallize slowly and give molded articles with a resin rich
glossy surface finish, inferior mechanical properties and slow molding
cycles, or to rapidly crystallize, giving molded articles with good
mechanical properties and short molding cycles but low gloss surface
finish. One method of improving surface gloss is to increase the mold
temperature but this can result in longer cooling times. It is also known
that molding wet polyethylene terephthalate produces parts with good gloss
but poor mechanical properties.
It is difficult to make fiber reinforced polyethylene terephthalate molding
compositions which will rapidly crystallize and which give molded articles
which display high surface gloss and good physical and mechanical
properties. Processability, shorter cycle times and better flow properties
are important. Thus, even when a particular polyethylene terephthalate
molding composition is molded into articles which display both good
surface finish characteristics and some good strength characteristics, the
articles may not possess the combination of thermal, electrical and
mechanical properties required for many commercial applications. For
example, in engineering resin applications, a glass fiber reinforced
polyethylene terephthalate molding composition needs to have good spiral
flow and rapid crystallization; it should provide molded articles with
attractive surface appearance, high heat distortion temperature and
minimal warpage after the part is removed from a mold.
There is a need for reinforced polyethylene terephthalate molding
compositions from which can be made articles with high surface gloss and
engineering resin performance characteristics. Also, there is a need for
compositions of this type which display high flow rates under molding
conditions without water addition and without lubricant addition. In
addition, these compositions should also be capable of having a flame
retardant material added thereto in an amount effective for achieving
flame retardancy without a significant change in the combination of
properties exhibited by articles molded from the composition. There is
also a need for compositions of this type which can be colored without
significantly changing properties of the composition or articles molded
from the composition while retaining good processability.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a new and improved class
of reinforced polyethylene terephthalate molding compositions which have
rapid crystallization, good processability, good flow rates, and from
which can be made molded articles having an excellent combination of good
surface gloss, good physical and mechanical properties and high heat
distortion temperatures.
Another object is to provide such a composition which can be readily
prepared by melt extrusion.
Another object is to provide a reinforced polyethylene terephthalate
molding composition which has good processability, is rapidly
crystallizable, has outstandingly high flow rates under molding
conditions, and which can be molded into articles having good surface
gloss and engineering resin performance charactertistics.
Another object is to provide such a composition which can be flame retarded
by the addition of additives which when so added do not cause a
significant change in desired properties.
Another object is to provide such a composition which can be colored by the
addition of additives which when so added do not cause a significant
change in desired properties.
Another object is to provide processes for making and using such
compositions.
Another object is to provide articles made from such compositions.
In accordance with one embodiment of this invention, a molding composition
which has a high injection molding flow rate and which can be molded into
articles with a glossy surface and engineering resin performance
characteristics comprises:
(a) polyethylene terephthalate;
(b) filler;
(c) an aliphatic polyester having a number average molecular weight in the
range from about 7,500 to about 20,000 and which is a condensation product
of an alkanedioic acid containing from 8 to about 12 carbon atoms per
molecule and an alkanediol containing from 2 to about 5 carbon atoms per
molecule;
(d) a metal salt of an ionic hydrocarbon copolymer of an alpha-olefin
containing from 2 to about 5 carbon atoms per molecule and an
alpha,beta-ethylenically unsaturated carboxylic acid containing from 3 to
about 5 carbon atoms per molecule in which copolymer the neutralized
anionic carboxyl groups are associated with cations of said metal, said
copolymer having a number average molecular weight in excess of about
3,000 prior to neutralization, said metal being selected from the group
consisting of sodium and potassium;
(e) an antioxidant; and
(f) a secondary amide described by the formula:
##STR1##
wherein R.sub.1 and R.sub.2 may be the same or different and represent
alkyl groups or unsaturated aliphatic groups containing from 8 to 36
carbon atoms and preferably 12 to 22 carbon atoms, and wherein each said
unsaturated group can have up to three double bonds.
Optionally, the inventive compositions may be flame retarded and/or
colored.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to a class of new and very useful molding
compositions of reinforced polyethylene terephthalate which have a high
flow rate under molding conditions, good mold release characteristics, a
rapid crystallization rate after being injection molded, and can be molded
into articles which have a surprising and unexpectedly good surface finish
as well as acceptable engineering resin performance characteristics, such
as good physical strength and high heat distortion temperature.
A good surface finish, among other advantages, is useful for the
fabrication of parts where visual appearance is important, such as
exterior automotive, motorcycle, bicycle, appliance and furniture parts.
Among other advantages, a high molding flow rate permits an injected resin
to fill all cavities of an intricate mold, as those skilled in the art
readily appreciate. A blended, melt-extruded, pelletized composition of
this invention can be conventionally injection molded, for example, using
an injection molding temperature range from about 520.degree. to
580.degree. F. into molds typically ranging in surface temperature from
about 180.degree. to about 280.degree. F.
In addition, articles made from the molding compositions of this invention
retain to an unexpected and remarkable extent an acceptable combination of
physical and mechanical properties when one or more of a selected class of
secondary amides are included in the compound. This result from use of
secondary amides is particularly unexpected because primary amides are
known to compromise physical properties when used to produce good gloss.
Secondary amides surprisingly can be used to improve gloss without causing
significant loss of desired physical properties. Deyrup (Re 32,334)
teaches that secondary amides in polyethylene terephthalate give molded
articles a rough surface finish.
More particularly, the molding resin compositions of this invention
generally comprise:
(a) from about 30 to about 90 weight percent, more preferably from 35 to 65
weight percent, based on total weight of the composition, of polyethylene
terephthalate having an intrinsic viscosity of at least about 0.25;
(b) from about 5 to about 65 weight percent, more preferably from 10 to 60
weight percent, based on total weight of the composition, of a filler;
(c) from about 0.5 to about 15 pph resin, more preferably from 2.5 to 10
pph resin, of an aliphatic polyester having a number average molecular
weight ranging from about 7,500 to about 20,000 and which is a
condensation product of an alkanedioic acid containing from 8 to about 12
carbon atoms per molecule and an alkanediol containing from 2 to about 5
carbon atoms per molecule;
(d) from about 0.1 to about 3 pph resin, more preferably 0.2 to 1.2 pph
resin, of a metal salt of an ionic hydrocarbon copolymer of an
alpha-olefin containing from 2 to 5 carbon atoms per molecule and an
alpha,beta-ethylenically unsaturated carboxylic acid containing from 3 to
about 5 carbon atoms per molecule in which copolymer the neutralized
anionic carboxyl groups are associated with cations of said metal, said
polymer having a molecular weight before such neutralization of at least
about 3,000, said metal being selected from the group consisting of sodium
and potassium;
(e) from about 0.01 to about 2 pph resin, more preferably from 0.2 to 1.0
pph resin, of an antioxidant; and
(f) from about 0.1 to about 5 pph resin, more preferably from about 0.5 to
about 3 pph resin, most preferably 1 to 3 pph resin, of a secondary amide
described by the formula:
##STR2##
wherein R.sub.1 and R.sub.2 may be the same or different and represent
alkyl groups or unsaturated aliphatic groups containing from 8 to 36
carbon atoms and preferably 12 to 22 carbon atoms, and wherein each said
unsaturated group can have up to three double bonds.
By "pph resin" or "pphr" as used herein is meant the parts by weight of
specified components per 100 parts by weight of polyethylene
terephthalate.
To flame retard a composition of this invention, one can admix therewith
from greater than 0 to about 50 pph resin, more preferably from about 25
to about 35 pph resin, of a composition consisting essentially of:
(i) brominated polystyrene having a number average molecular weight ranging
from about 10,000 to about 400,000, and having a bromine content in the
range from about 55 to about 75 weight percent (based on total weight of
the brominated polystyrene), and
(ii) antimonate of at least one metal selected from Group I, Group II, and
Group VII of the Periodic Table; wherein the weight ratio of said
brominated polystyrene to said antimonate ranges from about 2:1 to about
12:1, and more preferably, from about 3:1 to about 10:1.
Other flame retardants are also contemplated as useful in this invention.
To color a composition of this invention, one can admix therewith from
greater than 0 to about 10 weight percent, more preferably from about 0.05
weight percent to about 8 weight percent, based on total weight of the
composition, of a colorant. The amount of colorant which is preferable
will vary widely, depending on the widely varying concentrations in the
colorants available.
The Polyethylene Terephthalate
The polyethylene terephthalate employed herein generally has an inherent
viscosity of at least about 0.25, preferably about 0.4 as measured by ASTM
D-2857. The polyethylene terephthalate perferably has an upper limit on
inherent viscosity of about 1.2. Inherent viscosity is measured in a 3:1
volume ratio of methylene chloride and trifluoroacetic acid at 30.degree.
C. The term "polyethylene terephthalate" as used herein is used generally
to include high molecular weight polymers made by condensing ethylene
glycol with terephthalic acid or dimethylterephthalate no matter how
prepared. This term is meant to include polyethylene terephthalate
polymers which are modified by the inclusion of minor amounts, e.g., less
than about 20 percent by weight of the polymer, of comonomers or modifying
agents. Such comonomers or modifying agents include various diols such as
1,4-butanediol, cyclohexane dimethanol, diethylene glycol, polyalkylene
oxide, neopentyl glycol, butylene glycol, and 1,3-propanediol or mixtures
of two or more diols. Likewise, such comonomers or modifying agents can
include various diacids such as isophthalic acid, adipic acid, sebacic
acid, 2,6-naphthalene dicarboxylic acid and p-hydroxy benzoic acid.
Mixtures of two or more diacids may be used. Mixtures of polyethylene
terephthalate resins can be used. Suitable polyethylene terephthalate
polymers are commercially available.
Filler
Conventional fillers known in the art can be used. Examples of non-fibrous,
inorganic fillers include clay, mica, talc, kaolin, calcium carbonate,
barytes, ceramic spheres, glass spheres, glass flakes, calcium silicate,
and the like. Mixtures of two or more non-fibrous inorganic fillers can be
used.
Examples of non-fibrous organic fillers include wood and shell flours,
starches, carbohydrate by-products, synthetic organics, such as
polyvinylidene chloride spheres, and the like. Mixtures of two or more
non-fibrous ogranic fillers can be used.
Examples of metal powders, flakes, or fibers include aluminum, bronze,
zinc, nickel, stainless steel, and the like. Mixtures of two or more metal
can be used. Oxides of metals such as titanium dioxide, zinc oxide, and
the like are also contemplated as useful. Mixtures of two or more metal
oxides can be used. Also, mixtures of metals and metal oxides can be used.
Examples of fibrous fillers include those comprised of aramid, carbon,
glass, hybrids (such as aramid/carbon, aramid/carbon/glass, aramid/glass,
carbon/glass, and the like), boron, ceramic, metal, Wollastonite, mixtures
thereof and the like.
Mixtures of organic and inorganic fillers can be used. Also useful are
mixtures of fibrous and non-fibrous fillers, including such combinations
as glass fibers and glass flakes, glass fibers and mica, glass fibers and
Wollastonite, glass fibers and glass spheres, and the like. Metal fillers,
metal oxide fillers and mixtures of these can be combined with other
fibrous or non-fibrous fillers or with other organic or inorganic fillers
or with various mixtures of fillers from these categories.
When mixtures of more than one filler are used, the proportionate amounts
of the fillers will vary according to the form and properties of the
fillers and according to the properties desired in the articles to be made
from the polyethylene terephthalate molding composition. For example, in a
composition comprising:
(a) from about 30 to about 90 weight percent based on total weight of the
composition of polyethylene terephthalate;
(b) from about 5 to about 65 weight percent, based on total weight of the
composition, of filler;
(c) from about 0.5 to about 15 pph resin of an aliphatic polyester;
(d) from about 0.1 to about 3 pph resin of a metal salt of an ionic
hydrocarbon copolymer;
(e) from about 0.01 to about 2 pph resin of an antioxidant;
(f) from about 0.1 to about 5 pph resin of a secondary amide; the filler
can comprise a mixture of mica and fiber glass having a ratio of mica to
fiber glass from about 10:1 to about 1:10.
The glass fibers presently preferred have an average cross-sectional
thickness in the range from about 7 to 15 microns, preferably from about 8
to about 10 microns and an average length in the range from about 2 to
about 8 millimeters, preferably from about 2.5 to about 5 millimeters.
Such glass fibers are commercially available.
The Aliphatic Polyester
The aliphatic polyesters have a number average molecular weight in the
range from about 7,500 to about 20,000, preferably about 8,000 to about
10,000 and comprise condensation products of alkanedioic acids containing
from 8 to about 12 carbon atoms per molecule and alkanediols containing
from 2 to about 5 carbon atoms per molecule. Preferred alkanedioic acid
comonomers for such polyesters contain 8 to 10 carbon atoms per molecule
and preferred alkanediol comonomers for such polyesters contain 3 to 4
carbon atoms per molecule. One presently most preferred such polyester is
a condensation product of sebacic acid and 1,2-propanediol.
Characteristically, the aliphatic polyester is liquid at ambient
conditions.
The Ionic Hydrocarbon Copolymer
The ionic hydrocarbon copolymer contemplated as useful is a metal salt of
an ionic hydrocarbon copolymer of an alpha-olefin containing from 2 to
about 5 carbon atoms per molecule and an alpha,beta-ethylenically
unsaturated carboxylic acid containing from 3 to about 5 carbon atoms per
molecule in which copolymer the neutralized anionic carboxyl groups are
associated with cations of the metal with the copolymer having a number
average molecular weight in excess of about 3,000 prior to neutralization,
and with the metal being selected from the group consisting of sodium and
potassium.
Representative ionic hydrocarbon copolymers comprise the sodium and/or
potassium salts of copolymers of olefins (especially ethylene) with
acrylic acid, methacrylic acid, or mixtures thereof which are at least
about 30 percent neutralized. Suitable copolymers are commercially
available.
The aliphatic polyester and the ionic hydrocarbon copolymer (also known as
ethylene acid copolymer or ionomer) in combination with polyethylene
terephthalate induce rapid crystallization of the polyethylene
terephthalate so that melt injection of the composition into a mold having
a surface temperature of about 110.degree. C. results in molded products
with good properties. Typical cycle times at such a mold temperature are
characteristically not more than about 30 seconds.
The Antioxidant
Many different antioxidants can be used. In general, preferred antioxidants
are thermally stable at the processing temperature employed. Hindered
phenol antioxidants are presently preferred. The antioxidant which is
presently most preferred is available from Ciba-Geigy Corporation as
"Irganox 1010", the active component of which is believed to be tetrakis
(methylene 3-[3,5-di-t-butyl-4-hydroxyphenyl] propionate) methane. Other
suitable antioxidants include:
(A) Borg Warner's "Ultranox 626", the active agent of which is
bis[2,4-di-t-butyl phenyl pentaerythritol] diphosphite;
(B) Ciba-Geigy's "Irganox 259", the active agent of which is
1,6-hexamethylene bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamate) and/or
1,6-hexamethylene bis(3-[3,5-di-t-butyl-4-hydroxyphenyl]-propionate);
(C) Ferro Corporation's "Oxi-Chek 116", the active agent of which is
octadecyl 3,5-di-t-butyl-4-hydroxy-hydrocinnamate; and
(D) Ciba-Geigy's "Irganox 1098", the active agent of which is
N,N'-hexamethylene bis[3,5-di-t-butyl-4-hydroxy-hydrocinnamide].
The Secondary Amides
The secondary amides which can be employed herein are those described by
the formula:
##STR3##
wherein R.sub.1 and R.sub.2 may be the same or different and represent
alkyl groups or unsaturated aliphatic groups containing from 8 to 36
carbon atoms and preferably 12 to 22 carbon atoms, and wherein each said
unsaturated group can have up to three double bonds.
Examples of secondary fatty amides suitable for use herein include, but are
not limited to, N-stearyl stearamide, N-stearyl erucamide, N-erucyl
erucamide, N-oleyl palmitamide, N-oleyl hydroxypalmitamide, N-stearyl
oleamide, N-erucyl stearamide, N-oleyl oleamide, N-palmityl palmitamide,
N-behenyl behenamide, N-behenyl erucamide, N-oleyl stearamide, N-oleyl
behenamide, N-erucyl behenamide, N-capryl stearamide, N-lauryl
myristamide, N-margaryl arachidamide, N-tricosanyl nonadecanamide and the
like. Mixtures of two or more secondary amides can also be used. Preferred
secondary fatty amides include N-stearyl stearamide, N-oleyl palmitamide,
and N-erucyl erucamide, which are commercially available as Kemamide.TM.
S-180, Kemamide.TM. P-181 and Kemamide.TM. E-221, respectively.
The Flame Retardant
In the present application, the presently preferred flame retardant
comprises brominated polystyrene with an antimonate synergist.
The Brominated Polystyrene
Preferably, the bromine content of the brominated polystyrene is at least
about 60 weight percent of such polymer. Preferably, such polymer has a
number average molecular weight ranging from about 10,000 to about
400,000, preferably about 225,000 to about 350,000. Such brominated
polystyrenes are available commercially.
For purposes of achieving flame retardancy, the combined weight of the
brominated polystyrene and the antimonate (see below) in a resin blend is
preferably at least about 4 weight percent of the total resin blend. A
presently preferred weight ratio of brominated polystyrene to antimonate
compound(s) is from about 3:1 to about 10:1.
The Antimonate
A presently particularly preferred antimonate is sodium antimonate although
zinc antimonate and nickel antimonate and mixtures thereof are also
preferred. The antimonate is usually employed in a finely-divided
particulate or powder form.
Other Additives
Optionally, to increase impact strength, compositions of this invention can
additionally contain from greater than 0 to about 5 weight percent of a
polymeric epoxy compound of the type comprised of a condensation product
of bisphenol A with epichlorohydrin. The average number of repeating units
of bisphenol A/epichlorohydrin per molecule in such a condensate can range
from about 0.1 to about 20. Such polymeric epoxy compositions are
commercially available. Examples include the trademarked products "Epon
828," "Epon 1001F," and "Epon 1009F" available from Shell Chemical
Company.
The compositions of this invention can also optionally contain an amount of
polyethylene sufficient to obtain physical properties tailored for
particular applications or to improve processability, if desired.
Presently preferred is from greater than zero to about 10 pph resin.
Preferably the polyethylene has a molecular weight ranging from about 600
to 3,000. Such polymers are commercially available. Examples include the
trademarked materials "Epolene N34" or "Epolene C-10" from Eastman
Chemical Company and "Polywax 500", "Polywax 655", and "Polywax 1000" from
Petrolite Specialties Polymers Group.
In addition to the components discussed herein, the compositions of this
invention may contain other additives commonly employed (and in the
quantities known to the art or sufficient to achieve the desired result)
with polyethylene terephthalate. Examples include colorants such as carbon
black or blue concentrate, heat and ultraviolet light stabilizers, and the
like. Usually, the total quantity of such other additives is not more than
about 20 weight percent of the total weight of the composition, although
higher amounts could be used if desired.
Preparation
The compositions of this invention are prepared by blending together the
components by any convenient means. For example, dry polyethylene
terephthalate can be dry mixed in any suitable blender or tumbling means
with the other components and the resulting mixture melt-extruded.
Alternatively, all components except the glass or other filler can be
mixed by conventional means and the glass or other filler then added to
the already molten resin mixture. Preferably, the polyethylene
terephthalate is preblended with the glass fibers and then dry mixed with
the other additives before melt-extrusion. A convenient melt-extrusion
temperature range is about 520.degree. to 580.degree. F. The extrudate is
preferably in a strand form which can be chopped into pellets or the like
as desired.
Composition
The molding resin compositions of this invention are summarized in the
following Table 1:
TABLE 1
______________________________________
Polyethylene Terephthalate Molding Resin Compositions
Amounts
Broad Preferred
Component Range Range
______________________________________
Polyethylene Terephthalate, wt %.sup.a
30-90 35-65
Fillers, wt %.sup.a 5-65 10-60
Aliphatic Polyester, pph resin
0.5-15 2.5-10
Ionic Hydrocarbon Copolymer, pph resin
0.1-3 0.2-1.2
Antioxidant, pph resin 0.01-2 0.2-1.0
Secondary Amide, pph resin
0.1-5 0.5-3
Flame Retardant.sup.b,c, pph resin
0-50 25-35
Colorants.sup.b, wt. %.sup.a
0-10 0.05-8
Other Additives.sup.b, wt %.sup.a
0-20
______________________________________
.sup.a Based on total weight of the composition.
.sup.b Optional.
.sup.c This includes the brominated compound and the antimony synergist.
EXAMPLES
The following examples describe the invention and should be taken as
illustrative and not restrictive.
Components
Runs were made using the various combinations and amounts of ingredients
shown in the following examples.
Compounding
The polyethylene terephthalate resin was vacuum dried for about 16 hours at
250.degree. F. prior to compounding. Other dessicant or dehumidifing
drying methods are acceptable. The dry resin was removed from the drying
oven, then quickly tumble blended with the other ingredients prior to
compounding in a 1.5 inch 24:1 l/d Davis Standard extruder equipped with a
single stage mixing screw and strand die. The melt temperature range was
about 520.degree. to 540.degree. F. The mixture was either flood fed or
metered to the extruder using a volumetric feeder. A nitrogen blanket was
used to protect the polyethylene terephthalate resin from moisture
absorption in the feeder or hopper. The extruded strands were briefly
quenched in a water bath, allowed to dry using latent heat, and pelletized
into approximately 1/8 inch pellets.
Molding
The pelletized compositions were dried overnight in a dehumidifing oven at
225.degree. F. prior to injection molding. Test specimens were molded in
standard molds on a 55-ton hydraulic clamp 2.9 ounce injection molding
press, with a mold surface temperature of about 235.degree. F. and a
cylinder temperature of about 540.degree. F. The dry molding composition
was protected from moisture by a dry nitrogen blanket on the machine
hopper. A fast injection speed was used with about 5-second injection
time, about 4-second hold time, and about 25-second cooling time.
Injection pressure was adjusted for mold filling. Holding pressure was
about 80% of injection pressure.
Property Testing
Spiral flow measurements were done on a 0.250 in. .times.0.060 in. spiral
flow mold in a 55-ton injection molding machine. Mold surface temperature
was about 235.degree. F. and melt temperature was about 540.degree. F. A
fast injection speed was used with an injection time of about 5 seconds,
no hold time, and about 17 seconds cooling time. The average flow length
of 10 parts was taken after the machine had stabilized. Measurements were
taken at hydraulic pressures of about 500, 1000, and 1500 psi which
corresponded to injection pressures of about 6,750, 13,500, and 20,250
psi.
Surface appearance was visually rated on test parts molded under the
conditions described above. Scanning electron microscope photomicrographs
with a 100x magnification were made of the surfaces of parts molded from
two of the inventive compositions and from two control compositions.
Surface appearance ranged from dull to glossy.
The properties of molded test specimens were determined by ASTM procedures.
EXAMPLE 1
This example describes two inventive compositions and a third composition
which does not contain a gloss improver additive. The compositions are
designated, as A, B and C. Table 2 lists the components and the amounts of
each in the compositions. Footnotes to Table 2 further identify the
components and indicate commercial sources.
The inventive compositions A and B in Table 2 contain, respectively, 0.3
weight percent N-stearyl stearamide (Kemamide.TM. S-180) and 0.3 weight
percent N-erucyl erucamide (Kemamide.TM. E-221). The major component in
Kemamide.TM. E-221 is N-13-docosenyl-13-docosenamide. These commercially
available secondary amides are responsible for enhancing the surface gloss
of molded articles made from the inventive compositions A and B.
The remaining components of the compositions in Table 2 comprise
polyethylene terephthalate resin, glass fiber filler, mica filler,
nucleating agent, antioxidant and plasticizer.
The designation "weight percent" indicates the weight percent of the
various components based on the total weight of the composition. The
designation "pphr" indicates the parts by weight of the specified
components per 100 parts by weight of the resin.
TABLE 2
______________________________________
Polyethylene Terephthalate Compositions with
Secondary Amide Glass Improvers
A B C
Invention
Invention
Blank
______________________________________
Polyethylene Terephthalate.sup.a, wt. %
58.3 58.3 58.6
Glass.sup.b, wt. % 15.0 15.0 15.0
Mica.sup.c, wt. % 20.0 20.0 20.0
Formion .TM. 105.sup.d, wt. %
0.6 0.6 0.6
Irganox .TM. 1010.sup.e, wt. %
0.6 0.6 0.6
Paraplex .TM. G-25.sup.f, wt. %
4.2 4.2 4.2
Kemamide .TM. S-180.sup.g, wt. %
0.3
Kemamide .TM. E-221.sup.h, wt. %
0.3
Black Color Concentrate.sup.i, wt. %
1.0 1.0 1.0
______________________________________
.sup.a Polyethylene Terephthalate is Traytuf .TM. 5900 commercially
available from Goodyear.
.sup.b Glass fiber is 993 commercially available from Certainteed.
.sup.c Mica is KMG 40K Mica commercially available from KMG Minerals,
Inc., Kings Mountain, N.C.
.sup.d Ionic hydrocarbon copolymer commercially available from A.
Schulman, Inc.
.sup.e Antioxidant commercially available from CibaGeigy Corporation.
.sup.f Aliphatic Polyester commercially available from C. P. Hall.
.sup.g Stearyl stearamide commercially available from Humko Chemical
Division of Witco Corporation.
.sup.h Erucyl erucamide commercially available from Humko Chemical
Division of Witco Corporation.
.sup.i Black color concentrate is 21% carbon black in polyethylene
terephthalate commercially available from Reed Plastics as CPET 01333.
EXAMPLE 2
This example shows the physical and mechanical properties of molded
articles prepared from two inventive compositions and a third composition
which does not contain a gloss improver additive. The compositions are
designated, as A, B and C in Table 3. These compositions are the same as
those shown in Example 1 and Table 2.
Attention is called to the enhanced surface appearance of the samples
molded from the inventive compositions A and B. The rating of "glossy" was
assigned by visual observation to molded samples from A and B, whereas the
surface of molded samples from the composition C (containing no gloss
improver) was rated as "dull". This difference in surface appearance is
attributable to the presence of the secondary amides in inventive
compositions A (N-stearyl stearamide additive) and B (erucyl erucamide
additive).
It is noteworthy that, in general, properties other than surface appearance
in the properties of molded samples from all three compositions A, B and C
were comparable.
TABLE 3
______________________________________
Physical and Mechanical Properties of Polyethylene
Terephthalate Compositions with Secondary Amides
A.sup.a
B.sup.a C.sup.b
Invention
Invention
Blank
Weight %
______________________________________
Polyethylene Terephthalate.sup.c
58.3 58.3 58.6
Glass.sup.d 15.0 15.0 15.0
Mica.sup.e 20.0 20.0 20.0
Formion .TM. 105.sup.f
0.6 0.6 0.6
Irganox .TM. 1010.sup.g
0.6 0.6 0.6
Paraplex .TM. G-25.sup.h
4.2 4.2 4.2
Kemamide .TM. S-180.sup.i
0.3
Kemamide .TM. E-221.sup.j 0.3
Black Color Concentrate.sup.k
1.0 1.0 1.0
Physical
Flow rate, 68 68 64
g/10 min. at 275.degree. C. 5 Kg
DSC Measurements, .degree.C.
Tg 77 80 79
Tcc 125 125 125
Tm 252 253 251
Tmc 209 209 208
Crystallization Window, wt. %
48 49 48
Heat Distortion Temperature, .degree.C.
198 196 189
@ 1820 KPa
Surface glossy glossy dull
Mechanical
Tensile Break, KSI 13.1 13.1 12.8
Tensile Elongation, %
3.5 3.5 3.3
Flexural Strength, KSI
20.1 20.5 20.2
Flexural Modulus, MSI
1.3 1.3 1.3
Izod Impact
Notched Ft. Lb./In.
0.8 0.8 0.8
Unnotched Ft. Lb./In.
5.6 5.4 5.3
______________________________________
Notes for Table 3
.sup.a A and B contain secondary amide additives.
.sup.b C contains no gloss improver additive.
.sup.c Polyethylene terephthalate is Traytuf .TM. 5900 commercially
available from Goodyear.
.sup.d Glass fiber is 993 commercially available from Certainteed.
.sup.e Mica is KMG 40K Mica commercially available from KMG Minerals,
Inc., King's Mountain, N.C.
.sup.f Ionic hydrocarbon copolymer commercially available from A.
Schulman, Inc.
.sup.g Antioxidant commercially available from CibaGeigy Corporation.
.sup.h Aliphatic Polyester commercially available from C. P. Hall.
.sup.i Stearyl stearamide commercially available from Humko Chemical
Division of Witco Corporation.
.sup.j Erucyl erucamide commercially available from Humko Chemical
Division of Witco Corporation.
.sup.k Black color concentrate is 21% carbon black in polyethylene
terephthalate commercially available from Reed Plastics as CPET 01333.
EXAMPLE 3
This example presents the electrical properties of molded articles prepared
from two inventive compositions and a third composition which does not
contain a gloss improver additive. The compositions are A, B and C and are
the same compositions as those shown as A, B and C in Examples 1 and 2.
It is noteworthy that the inventive compositions A and B gave molded
samples which exhibited comparable electrical properties to samples molded
from composition C which contained no gloss improver. The A, B and C
systems gave similar results in spiral flow values and hydrolytic
stability testing (see Table 4).
It can be concluded from the information in Examples 1, 2 and 3 that the
incorporation of secondary amides such as N-stearyl stearamide and erucyl
erucamide into the polyethylene terephthalate molding compositions
ultimately results in molded articles exhibiting an excellent glossy
appearance without sacrificing any performance in physical, mechanical and
electrical properties.
TABLE 4
______________________________________
Physical and Electrical Properties of Polyethylene
Terephthalate Compositions with Gloss Improvers
A.sup.a
B.sup.a C.sup.b
Invention
Invention
Blank
______________________________________
Polyethylene Terephthalate.sup.c,
58.3 58.3 58.6
wt. %
Glass.sup.d, wt. %
15.0 15.0 15.0
Mica.sup.e, wt. % 20.0 20.0 20.0
Formion .TM. 105.sup.f, wt. %
0.6 0.6 0.6
Irganox .TM. 1010.sup.g, wt. %
0.6 0.6 0.6
Paraplex .TM. G-25.sup.h. wt. %
4.2 4.2 4.2
Kemamide .TM. S-180.sup.i, wt. %
0.3
Kemamide .TM. E-221.sup.j, wt. %
0.3
Black Color Concentrate.sup.k, wt. %
1.0 1.0 1.0
Dielectric Strength
1/16 in., Volts/mil
623 635 641
Dielectric Constant
1 KHz 4.30 4.02 4.30
1 MHz 4.04 3.81 4.03
Dissipation Factor
1 KHz 0.019 0.017 0.0177
1 MHz 0.004 0.0038 0.0039
Resistivity
Volume, ohm/cm E + 15 E + 15 E + 15
Surface, ohm/sq cm
E + 14 E + 14 E + 14
Insulation Resistance
E + 11 E + 11 E + 11
Arc Resistance, Seconds
137 138 138
Arc Tracking Rate
Spiral Flow, In. at
6,750 PSI 91/4 101/4 9
13,500 PSI 133/4 141/4 131/2
20,250 PSI 171/2 181/4 17
Hydrolytic Stability,
% Tensile at
160.degree. F. 21 day
77 78 74
95% relative humidity
______________________________________
Notes for Table 4
.sup.a A and B contain secondary amide additives.
.sup.b C contains no gloss improver additive.
.sup.c Polyethylene terephthalate is Traytuf .TM. 5900 commercially
available from Goodyear.
.sup.d Glass fiber is 993 commercially available from Certainteed.
.sup.e Mica is KMG 40K Mica commercially available from KMG Minerals,
Inc., Kings Mountain, N.C.
.sup.f An ionic hydrocarbon copolymer commercially available from A.
Schulman, Inc.
.sup.g Antioxidant commercially available from CibaGeigy Corporation.
.sup.h An Aliphatic Polyester commercially available from C. P. Hall.
.sup.i Stearyl stearamide commercially available from Humko Chemical
Division of Witco Corporation.
.sup.j Erucyl erucamide commercially available from Humko Chemical
Division of Witco Corporation.
.sup.k Black color concentrate is 21% carbon black in polyethylene
terephthalate commercially available from Reed Plastics as CPET 01333.
EXAMPLE 4
This example demonstrates that the secondary amide additives of the
inventive compositions cannot be replaced with related primary amides.
Although essentially no difference can be seen in the mechanical properties
of the molded articles at the 0.5 pphr level of the different amide-type
additives (see "Test Results" in Table 5 and Table 6), at the 1.0 pphr
additive level the secondary amide additives are superior to the primary
amide additives.
Referring to the results shown in Tables 5 and 6, at the 0.5 pphr amide
additive level the flexural strength and tensile break properties of
molded samples from the systems containing the different types of amides
were comparable.
However, referring to the results shown in Table 7 at the 1.0 pphr amide
additive level, the flexural strength and tensile break properties of
molded samples from the systems containing the primary amide additives
were significantly lower than the same properties of samples molded from
the inventive compositions containing the secondary amide additives.
It can thus be concluded from the data of Table 7 that the incorporation of
primary amides such as Kemamide.TM. E and Kemamide.TM. B into the
polyethylene terephthalate molding compositions at the 1.0 pphr levels
ultimately results in molded articles exhibiting reduced tensile break and
flexural strength properties compared to the properties of molded articles
made from analogous inventive compositions containing secondary amides.
This decrease in mechanical properties more than off-sets any enhancement
of gloss that might accompany the use of primary amide additives in
polyethylene terephthalate molding compositions.
TABLE 5
______________________________________
Comparison of Primary Amides and Secondary Amides
as Gloss Improvers in PET Compositions
A.sup.a
B.sup.b C.sup.a
Control
Invention
Control
Weight %
______________________________________
Polyethylene Terephthalate.sup.c
40.1 40.1 40.1
Glass.sup.d 55.0 55.0 55.0
Formion .TM. 105 0.4 0.4 0.4
Irganox .TM. 1010 0.4 0.4 0.4
Paraplex .TM. G-25
2.9 2.9 2.9
Kemamide .TM. E 0.2
Kemamide .TM. E-221 0.2
Kemamide .TM. B 0.2
Black Color Concentrate.sup.e
1.0 1.0 1.0
Test Results
Flex Modulus, MSI 2.6 2.6 2.6
Flex Strength, KSI
37.5 39.0 37.7
Tensile Break, KSI
24.5 25.5 24.0
% Elongation 3.4 3.7 3.6
______________________________________
.sup.a A and C contain primary amide additives (controls).
.sup.b B contains secondary amide additive.
.sup.c Polyethylene terephthalate is Traytuf .TM. 5900 commercially
available from Goodyear.
.sup.d Glass fiber is 93B commercially available from Certainteed.
.sup.e Black color concentrate is 21% carbon black in polyethylene
terephthalate commercially available from Reed Plastics as CPET 01333.
TABLE 6
______________________________________
Comparison of Primary Amides and Secondary Amides
as Gloss Improvers in PET Compositions
D.sup.a
E.sup.b F.sup.b G.sup.c
Control
Invention
Invention
Blank
Weight %
______________________________________
Polyethylene 40.1 40.1 40.1 40.3
Terephthalate.sup.d
Glass.sup.e 55.0 55.0 55.0 55.0
Kemamide .TM. B
0.2
Kemamide .TM. S-180 0.2
Kemamide .TM. E-221 0.2
Formion .TM. 105
0.4 0.4 0.4 0.4
Irganox .TM. 1010
0.4 0.4 0.4 0.4
Paraplex .TM. G-25
2.9 2.9 2.9 2.9
Black Color 1.0 1.0 1.0 1.0
Concentrate.sup.f
Test Results
Flex Modulus, MSI
2.6 2.7 2.8 2.5
Flex Strength, KSI
38.2 37.5 37.7 39.3
Tensile Break, KSI
24.6 24.2 24.3 25.7
% Elongation 3.6 3.6 3.4 3.7
______________________________________
.sup.a D contains primary amide additives (control).
.sup.b E and F contain secondary amide addivives.
.sup.c G contains no gloss improver additive.
.sup.d Polyethylene terephthalate is Traytuf .TM. 5900 commercially
available from Goodyear.
.sup.e Glass fiber is 93B commercially available from Certainteed.
.sup.f Black color concentrate is 21% carbon black in polyethylene
terephthalate commercially available from Reed Plastics as CPET 01333.
TABLE 7
__________________________________________________________________________
Comparison of Primary Amides and Secondary Amides
as Gloss Improvers in PET Compositions
H.sup.a
I.sup.b
J.sup.a
K.sup.b
L.sup.b
Control
Invention
Control
Invention
Invention
Weight %
__________________________________________________________________________
Polyethylene Terephthalate.sup.c
39.9 39.9 39.9 39.9 39.9
Glass.sup.d 55.0 55.0 55.0 55.0 55.0
Formion .TM. 105
0.4 0.4 0.4 0.4 0.4
Irganox .TM. 1010
0.4 0.4 0.4 0.4 0.4
Paraplex .TM. G-25
2.9 2.9 2.9 2.9 2.9
Kemamide .TM. E
0.4
Kemamide .TM. E-221
0.4 0.4
Kemamide .TM. B 0.4
Kemamide .TM. S-180 0.4
Black Color Concentrate.sup.e
1.0 1.0 1.0 1.0 1.0
Test Results
Flex Modulus, MSI
2.6 2.6 2.6 2.5 2.4
Flex Strength, KSI
32.3 38.3 31.8 37.6 38.3
Tensile Break, KSI
19.3 25.4 18.2 25.6 25.2
% Elongation 2.0 2.9 1.8 3.0 3.0
__________________________________________________________________________
.sup.a H and J contain primary amide additives (controls).
.sup.b I, K and L contain secondary amide additives.
.sup.c Polyethylene terephthalate is Traytuf .TM. 5900 commercially
available from Goodyear.
.sup.d Glass fiber is 93B commercially available from Certainteed.
.sup.e Black color concentrate is 21% carbon black in polyethylene
terephthalate commercially available from Reed Plastics as CPET 01333.
EXAMPLE 5
This example shows that the secondary amide additives of the present
invention can be used as gloss improvers in polyethylene terephthalate
molding compositions at levels of 1.0 pphr, 2.0 pphr and 3.0 pphr with no
detrimental effect on the mechanical properties of molded articles made
from the inventive molding compositions.
Referring to the "Test Results" in Table 8 it can been seen that for a
given secondary amide additive the measured mechanical properties of
molded articles were comparable at additive levels of 1.0 pphr, 2.0 pphr
and 3.0 pphr.
The secondary amide additives used in this example were (1) Kemamide.TM.
E-221 with a major portion of erucyl erucamide which is N-13-docosenyl
13-docosenamide, (2) Kemamide.TM. S-180 with a major portion of N-stearyl
stearamide which is N-octadecyl octadecanamide and (3) Kemamide.TM. P-181
with a major portion of N-oleyl palmitamide which is N-9-octadecenyl
hexadecanamide.
TABLE 8
__________________________________________________________________________
Varying Amounts of Secondary Amides as Gloss Improvers
in Polyethylene Terephthalate Compositions
M N O P Q R S T U V
Invention
Invention
Invention
Blank
Weight %
__________________________________________________________________________
Polyethylene Terephthalate.sup.d
39.9
39.9
39.9
39.5
39.5
39.5
39.1
39.1
39.1
40.3
Glass.sup.e 55.0
55.0
55.0
55.0
55.0
55.0
55.0
55.0
55.0
55.0
Formion .TM. 105
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
Irganox .TM. 1010
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
Paraplex .TM. G-25
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
Kemamide .TM. E-221
0.4 0.8 1.2
Kemamide .TM. S-180
0.4 0.8 1.2
Kemamide .TM. P-181 0.4 0.8 1.2
Black Color Concentrate.sup.f
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
Test Results
Flex Modulus, MSI
2.7
2.6
2.6
2.6
2.5
2.6
2.6
2.5
2.5
2.7
Flex Strength, KSI
33.0
32.9
31.7
31.9
33.0
30.8
32.6
34.2
33.0
34.5
Tensile Break, KSI
21.9
21.6
20.6
21.5
21.6
19.9
20.6
21.9
21.9
22.1
% Elongation 2.5
2.5
2.4
2.8
2.7
2.5
2.5
2.7
2.7
2.4
__________________________________________________________________________
.sup.d Polyethylene terephthalate is Traytuf .TM. 5900 commercially
available from Goodyear.
.sup.e Glass fiber is 93B commercially available from Certainteed.
.sup.f Black color concentrate is 21% carbon black in polyethylene
terephthalate commercially available from Reed Plastics as CPET 01333.
EXAMPLE 6
This example shows that the secondary amide additives of the present
invention can be used as gloss improvers in flame retarded polyethylene
terephthalate molding compositions in the absence of colorant. Molded
articles made from two such compositions exhibited a surface which was tan
colored and visually rated as "slightly dull". An analogous pair of
inventive compositions without colorant and without flame retardant gave
molded articles which exhibited a surface which was off-white and visually
rated as "glossy".
Referring to the results in A', B', E' and F' of Table 9 it can be seen
that the secondary amides Kemamide.TM. E-221 and Kemamide.TM. S-180
functioned as gloss improvers in polyethylene terephthalate compositions
containing 30 weight percent glass fiber and no colorant wherein the E'
and F' systems also contained a flame retardant.
Runs C' and D' in Table 9 further show the effectiveness of the secondary
amides as gloss improvers in polyethylene terephthalate compositions
containing no colorant and no flame retardant but with a higher level of
glass fiber at 45 weight percent. Molded articles from inventive
compositions C' and D' exhibited higher flexural strengths than did molded
articles made from inventive compositions A' and B'. This difference was
probably due to the higher glass loading in the C' and D' systems.
In all the runs of Table 9 the level of secondary amide gloss improvers was
1.0 pphr.
In the flame retarded compositions of Table 9, i.e., E' and F', a dramatic
increase in flow properties is evident as is somewhat of a decline in
flexural strength and tensile break values.
TABLE 9
__________________________________________________________________________
Secondary Amides as Gloss Improvers in Flame
Retarded Polyethylene Terephthalate Compositions
A' B' C' D' E' F'
Weight %
__________________________________________________________________________
Polyethylene Terephthalate
63.6
63.6
50.0
50.0
49.1
49.1
Glass 30.0
30.0
45.0
45.0
30.0
30.0
Formion .TM. 105
0.6
0.6
0.5
0.5
0.5
0.5
Irganox .TM. 1010
0.6
0.6
0.5
0.5
0.5
0.5
Paraplex .TM. G-25
4.6
4.6
3.5
3.5
3.5
3.5
Kemamide .TM. E-221
0.6 0.5 0.5
Kemamide .TM. S-180
0.6 0.5 0.5
Pyrochek .TM. 68PB 14.4
14.4
Sodium Antimonate 1.5
1.5
Test Results
Flex Modulus, MSI
1.5
1.5
2.1
2.2
1.6
1.6
Flex Strength, KSI
36.3
36.6
41.8
43.6
28.5
28.0
Tensile Break, KSI
22.4
22.9
21.8
23.0
18.9
18.1
% Elongation 5.1
5.4
3.2
3.7
4.0
3.5
Notched Izod, Ft. Lb./In.
1.6
1.5
1.8
1.8
1.1
0.9
Melt Flow, 48 45 38 40 92 92
g/10 min., 275.degree., 5 Kg
Spiral Flow, in., at
6,750 psi 73/4
8 61/4
61/2
101/4
101/2
13,500 psi 113/4
113/4
91/2
93/4
151/2
153/4
20,250 psi 141/4
141/4
113/4
113/4
191/2
193/4
Color off off off off tan tan
white
white
white
white
Surface glossy
glossy
slightly
slightly
slightly
slightly
dull
dull
dull
dull
__________________________________________________________________________
EXAMPLE 7
This example shows that the secondary amide additives of the present
invention can be used as gloss improvers in flame retarded polyethylene
terephthalate molding compositions in the presence of a colorant such as
carbon black. Molded articles made from two such compositions exhibited a
surface which was black and visually rated as "very slightly dull". An
analogous pair of inventive compositions without flame retardant but with
a carbon black colorant gave molded articles which exhibited a black
surface which was visually rated as "very slightly dull".
Referring to the results in G', H', K' and L' of Table 10 it can be seen
that the secondary amides Kemamide.TM. E-221 and Kemamide.TM. S-180
functioned as gloss improvers in polyethylene terephthalate compositions
containing 30 weight percent glass fiber and carbon black colorant wherein
the K' and L' systems also contained a flame retardant.
Runs I' and J' in Table 10 further show the effectiveness of the secondary
amides as gloss improvers in polyethylene terephthalate compositions
containing carbon black colorant and no flame retardant but with a higher
level of glass fiber at 45 weight percent. Molded articles from inventive
compositions I' and J' exhibited higher flexural strengths than did molded
articles made from inventive compositions G' and H'. This difference was
probably due to the higher glass loading in the I' and J' systems.
In all the runs of Table 10 the level of secondary amide gloss improvers
was 1.0 pphr.
In the flame retarded compositions of Table 10, i.e., K' and L', a rather
dramatic increase in flow properties is evident as is somewhat of a
decline in flexural strength and tensile break values.
TABLE 10
__________________________________________________________________________
Secondary Amides as Gloss Improvers in Flame
Retarded Polyethylene Terephthalate Compositions
with Carbon Black
G' H' I' J' K' L'
Weight %
__________________________________________________________________________
Polyethylene Terephthalate
62.6
62.6
49.0
49.0
48.1
48.1
Glass 30.0
30.0
45.0
45.0
30.0
30.0
Formion .TM. 105
0.6
0.6
0.5
0.5
0.5
0.5
Irganox .TM. 1010
0.6
0.6
0.5
0.5
0.5
0.5
Paraplex .TM. G-25
4.6
4.6
3.5
3.5
3.5
3.5
Kemamide .TM. E-221
0.6 0.5 0.5
Kemamide .TM. S-180
0.6 0.5 0.5
Pyrochek .TM. 68PB 14.4
14.4
Sodium Antimonate 1.5
1.5
Black Color Concentrate
1.0
1.0
1.0
1.0
1.0
1.0
Test Results
Flex Modulus, MSI
1.5
1.4
2.1
2.1
1.6
1.5
Flex Strength, KSI
33.7
33.6
39.1
39.2
28.3
27.9
Tensile Break, KSI
21.8
21.4
22.6
23.1
18.9
19.0
% Elongation 5.0
4.9
3.6
3.9
4.0
3.8
Notched Izod, Ft. Lb./In.
1.2
1.3
1.6
1.6
1.1
1.0
Melt Flow, 50 53 36 36 89 90
g/min., 275.degree. C., 5 Kg
Color black
black
black
black
black
black
Surface very
very
slightly
slightly
very
very
slightly
slightly
dull
dull
slightly
slightly
dull
dull dull
dull
__________________________________________________________________________
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